JP2016060880A - Hydrophilic thermosetting resin composition and hydrophilic molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrophilic thermosetting resin composition and hydrophilic molded article that has an excellent surface durability even in an environment under the influence of water such as high pressure water, as the appearance surface is removed by high pressure-water because of the high contact angle of polyester resin/styrene and epoxy resin/acid anhydride with respect to said resin cured product/water.SOLUTION: Provided is a thermosetting resin composition containing (A) an unsaturated polyester resin, (B) a reactive diluent comprising a hydroxy group and a carbon-carbon double bond, (C) a polymerization initiator, as essential components, or (D) a liquid bisphenol type epoxy resin, (E) a phenol resin hardener comprising a hydroxy group and a carbon-carbon double bond, and (F) a hardening accelerator, as essential component, and in which the contact angle of said hardened product surface with respect to water is 70 degrees or less.SELECTED DRAWING: None

Description

  The present invention relates to a hydrophilic thermosetting resin composition capable of obtaining a resin cured product whose surface is easily adapted to water, and a hydrophilic molded article produced using the same.

  Conventionally, polyester resins, epoxy resins, and the like have been used for the purpose of protecting coils for building materials and electronic parts used for floor and exterior wall coating. For washing floors and outer walls, there is an opportunity to be exposed to high-pressure water such as high-pressure washing water, and the water cooling method is also used to cool the coil. Opportunities are increasing.

  General polyester resin / styrene and epoxy resin / anhydride resin cured products have a high contact angle with water, so they tend to repel water. There is a possibility that the long-term reliability is inferior.

  In contrast, it is considered that long-term reliability can be improved by imparting hydrophilicity to the cured resin. Examples of a method for imparting hydrophilicity to a cured resin product include a method of treating a film surface by plasma treatment (for example, Patent Document 1), and a polymerizable unsaturated group-containing resin having a specific molecular weight range on the surface of a molded product. A method of forming a water-resistant coating film by coating a resin in a mold (for example, Patent Document 2) has been proposed.

JP 2005-223167 A JP 2013-184307 A

  However, in the method described in Patent Document 1, the surface modification effect by plasma treatment is not sustained, and the effect of improving durability over a long period of time is low. Moreover, in the method of patent document 2, since only a comparatively thin coating film is formed, it does not have sufficient tolerance to the load by high pressure water like the said washing | cleaning.

  Therefore, the present invention has been made to solve the above-described problems, and is a hydrophilic thermosetting resin that is a cured product having excellent surface durability even under an environment affected by water such as high-pressure water. An object is to provide a composition and a hydrophilic molded article.

  The inventors of the present invention have focused on the contact angle of the cured resin, found that the thermosetting resin composition having a specific contact angle on the surface of the cured product has excellent water resistance, and completed the present invention. It is.

  That is, the hydrophilic thermosetting resin composition of the present invention has an unsaturated polyester resin or an epoxy resin as a main component, and a contact angle with respect to water on the surface of the cured product is 70 degrees or less. More specifically, the unsaturated polyester resin comprises (A) an unsaturated polyester resin, (B) a reactive diluent having a hydroxyl group and a carbon-carbon double bond, and (C) a polymerization initiator. An essential component is a resin composition as an essential component, or (D) a liquid bisphenol-type epoxy resin, (E) a phenol resin curing agent having a hydroxyl group and a carbon-carbon double bond, and (F) a curing accelerator. The resin composition is preferably used.

  The hydrophilic molded article of the present invention is characterized by being molded by curing the hydrophilic thermosetting resin composition of the present invention. At this time, the substrate may be impregnated and then cured, and a fiber substrate is preferably used as the substrate.

  In the present invention, by reducing the contact angle with water on the surface of the cured resin, the surface of the cured resin is easily adapted to water, and the surface is eroded by contact with high-pressure water or the like. It is possible to obtain a molded product in which unevenness is less likely to occur. Since the molded product thus obtained has high resistance to water, the product life can be extended and long-term product reliability can be imparted.

  Hereinafter, the hydrophilic thermosetting resin composition and the hydrophilic molded article of the present invention will be described in detail.

[Hydrophilic thermosetting resin composition]
The hydrophilic thermosetting resin composition of the present invention is mainly composed of an unsaturated polyester resin or an epoxy resin, and has a contact angle with water on the surface of the cured product when the resin composition is cured. It is a resin composition which becomes 70 degrees or less. By making the contact angle with the water on the surface of the cured product 70 degrees or less, the impact when the water droplets and the surface of the cured product come into contact with each other during contact with high-pressure water or the like by washing is reduced. Damage can be suppressed and durability is improved. When this contact angle exceeds 70 degrees, the impact of high-pressure water droplets directly damages the surface of the cured product, and the surface of the cured product is easily damaged, resulting in a decrease in durability.

[Unsaturated polyester resin composition]
Examples of the resin composition that realizes such a contact angle include (A) an unsaturated polyester resin, (B) a reactive diluent having a hydroxyl group and a carbon-carbon double bond, and (C) a polymerization initiator. And a hydrophilic thermosetting resin composition having as essential components.

  The (A) unsaturated polyester resin used here is a known one obtained by mixing an acid component and an alcohol component and obtained by an esterification reaction.

  Examples of the acid component include α, β-unsaturated polybasic acid and saturated polybasic acid. Examples of the α, β-unsaturated polybasic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid and anhydrides thereof, and the saturated polybasic acid includes phthalic acid, phthalic anhydride, isophthalic acid, Examples include terephthalic acid, endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid, tetrabromophthalic acid, succinic acid, adipic acid, and sebacic acid. These acid components can be used alone or in admixture of two or more.

  Moreover, a polyhydric alcohol is mentioned as an alcohol component. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hydrogenated bisphenol A, 2,2-di (4-hydroxypropoxyphenyl) propane, glycerin, trimethylolethane, trimethylolpropane, trishydroxyethyl Examples include isocyanurate and pentaerythritol. These can be used alone or in admixture of two or more.

  Moreover, modification | denaturation components other than unsaturated polyester resin can be added to this (A) unsaturated polyester resin. Examples of the modifying component that can be used include linseed oil, coconut oil, soybean oil, tall oil and the like, and these can be used alone or in combination of two or more.

  As for the compounding quantity of this (A) unsaturated polyester resin, it is desirable to contain 20-90 mass% in a resin composition. If the blending amount is less than 20% by mass, the unsaturated polyester resin cannot obtain sufficient reactivity, and the mechanical strength of the cured product may be lowered. If the blending amount exceeds 90% by mass, workability and impregnation May be worse.

  The unsaturated polyester resin may be prepared by subjecting a predetermined raw material to a dehydration condensation reaction at about 150 to 230 ° C. while blowing an inert gas such as nitrogen in a reaction vessel. The reaction needs to be continued at least until the reaction system becomes transparent, and the acid value of the obtained unsaturated polyester resin is desirably 30 or less.

  Examples of the reactive diluent (B) used here include a reactive diluent having a hydroxyl group and a carbon-carbon double bond, and examples thereof include an acrylate monomer having a hydroxyl group. Examples of such acrylate monomers include 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate. These can be used alone or in admixture of two or more.

  As for the compounding quantity of this (B) reactive diluent, it is desirable to contain 5-70 mass% in a resin composition. When the blending amount is less than 5% by mass, the workability and impregnation are deteriorated. When the blending amount exceeds 70% by mass, the unsaturated polyester resin cannot obtain sufficient reactivity, and the mechanical strength of the cured product is lowered. There is a risk.

  Examples of the (C) polymerization initiator used here include known organic peroxides used for curing (A) unsaturated polyester resins. Examples of the organic peroxide include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters, and alkylperesters. Etc.

  As for the compounding quantity of this (C) polymerization initiator, 0.1-5 mass% is preferable in a resin composition. If it is less than 0.1% by mass, curing does not proceed sufficiently, and sufficient characteristics cannot be obtained, and if it exceeds 5% by mass, the pot life after mixing the curing agent at low temperature may be shortened.

〔Epoxy resin〕
Moreover, as another resin composition which implement | achieves a contact angle like this invention, for example, (D) Liquid bisphenol-type epoxy resin, (E) The phenol resin hardening | curing agent which has a hydroxyl group and a carbon-carbon double bond, (F) The hydrophilic thermosetting resin composition which has a hardening accelerator as an essential component is mentioned.

  The (D) liquid bisphenol type epoxy resin used here may be a known liquid type bisphenol type compound having two or more epoxy groups in one molecule, and is not particularly limited.

  Examples of the liquid bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and the like. Among them, bisphenol A type epoxy resin and bisphenol F type epoxy resin are suitable. . Such a liquid bisphenol type epoxy resin is available as a commercial product. For example, EP4100E [manufactured by ADEKA CORPORATION, trade name], # 828EL [manufactured by Mitsubishi Chemical Corporation, trade name], DOW331 [DOW (stock name)] Product name], R140P, R710 [Mitsui Petrochemical Co., Ltd. product name], and the like.

  As an epoxy resin used here, you may use together other epoxy resins other than (D) liquid bisphenol type epoxy resin. Here, the other epoxy resin may be one having two or more epoxy groups in one molecule, and is not particularly limited, such as a general-purpose epoxy resin or a solid epoxy resin. In addition to these, a liquid monoepoxy resin or the like can be used as necessary.

  When other epoxy resins are used in combination, when the epoxy resin used is 100% by mass, (D) the liquid bisphenol type epoxy resin is preferably contained in an amount of 50% by mass or more, more preferably 70% by mass or more. preferable. Moreover, it is preferable that the epoxy resin to be used is a liquid epoxy resin as a whole epoxy resin, and a liquid epoxy resin should just be a liquid at room temperature (25 degreeC) here.

  The phenol resin curing agent having (E) hydroxyl group and carbon-carbon double bond used here may be a phenol resin having a hydroxyl group and a carbon-carbon double bond, and has two or more hydroxyl groups in one molecule. Liquid phenolic resins are preferred.

  Examples of such (E) phenolic resin curing agent include allylphenol-formaldehyde resin (phenolic resin synthesized using allylphenol and formaldehyde as raw materials).

  The blending amount of this (E) phenol resin curing agent is 0.8 to 1.3 equivalents, preferably 0.85 to 1.2 equivalents of phenolic hydroxyl group with respect to 1 equivalent of the epoxy group of the (D) epoxy resin. Adjust to the extent. If it is less than 0.8 equivalent, curing will be insufficient, and if it exceeds 1.3 equivalent, the mechanical properties of the cured product may be reduced.

  Examples of the (F) curing accelerator used here include those known as epoxy resin curing accelerators, and (D) the action of promoting the reaction between the liquid bisphenol type epoxy resin and the (E) phenol resin curing agent. If it has, it can be used without particular limitation. Examples of such (F) curing accelerators include tertiary amines, quaternary ammonium salts, imidazoles, organic phosphines, Lewis acid catalysts, and the like. Specific examples of these compounds include imidazoles such as 2-ethyl-4-ethylimidazole and 1-cyanoethyl-2-ethyl-4-ethylimidazole, benzyldimethylamine, 2,4,6-tris. Tertiary amines such as (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and its octyl salt, triethylphosphine, triphenylphosphine, diphenylphosphine and the like. These (F) curing accelerators can be used alone or in admixture of two or more.

  It is preferable that the compounding quantity of this (F) hardening accelerator is the range of 1-5 mass parts with respect to 100 mass parts of the said (E) phenol resin hardening | curing agent. If the blending amount is less than 1 part by mass, the curing time may be long and the mechanical properties may not be sufficiently improved, and if it exceeds 5 parts by mass, the reaction is fast and the pot life is shortened.

(Additive)
The hydrophilic thermosetting resin composition of the present invention is a system having the above components (A) to (C) as essential components, or a system having the above components (D) to (F) as essential components. Additives can be blended as necessary, and examples of the additive include (G) filler.

  Here, examples of the filler (G) include known fillers added and blended in the resin composition, and are inorganic fillers such as silica sand, talc, silica, mica, clay glass, and core shell rubber. Is preferred. The filler (G) used here is preferably a filler having an average particle size of 10 to 500 μm, and more preferably a filler having a particle size of 50 to 200 μm. By blending such a filler, mechanical and physical properties such as low linear expansion and high strength of the resin composition can be imparted. These fillers can be used individually by 1 type or in mixture of 2 or more types.

In the present specification, the average particle diameter is a 50% particle diameter D ₅₀ calculated from a volume-based particle size distribution obtained by a laser diffraction / scattering method. At this time, the particle size distribution to be measured can be measured by a laser diffraction / scattering particle size distribution measuring device (for example, product name: CILAS 1064 manufactured by Cirrus).

  (G) The blending amount of the filler is preferably in the range of 1 to 10% by mass when the entire resin composition is 100% by mass, and the curing time is long when the blending amount is less than 1% by mass. There is a possibility that the mechanical properties cannot be sufficiently improved, and when it exceeds 10% by mass, the viscosity increases, which is not preferable from the viewpoint of workability.

  The surface of the filler (G) can be modified by adding a coupling agent to the resin composition in order to obtain further excellent insulation reliability and mechanical strength of the cured product. Examples of the coupling agent that can be used here include known coupling agents such as a silane coupling agent, a titanium coupling agent, and an aluminum coupling agent. Of these, a silane coupling agent is particularly preferable because of excellent properties such as moisture resistance, and an aminosilane coupling agent is more preferable.

  Examples of aminosilane coupling agents include 3-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-aminoethylaminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) butoxy) propyl-3-aminopropyltrimethoxysilane and the like can be mentioned, and these can be used alone or in combination of two or more. May be.

  Moreover, in the unsaturated polyester resin composition which has said (A)-(C) component as an essential component, unless it is contrary to the objective of this invention, cobalt, copper, lead, manganese as a hardening accelerator as needed, Metal soaps such as zinc and calcium, and hydroquinone, parabenzoquinone, methylhydroquinone, t-butylcatechol and the like can be appropriately added and blended as a polymerization inhibitor.

  Moreover, in the epoxy resin composition which has said (D)-(F) component as an essential component, unless it is contrary to the objective of this invention, an antifoamer, a leveling agent, etc. can be suitably added and mix | blended as needed. .

[Hydrophilic molded product]
The hydrophilic molded article of the present invention is a molded article obtained by curing and molding the above-described hydrophilic thermosetting resin composition of the present invention as it is or impregnating a base material and then curing the molded article. By covering the base material in this manner, the surface of the molded product is covered with a cured resin having a contact angle with water of 70 degrees or less, and durability by contact with high-pressure water is improved.

  Here, the substrate is not particularly limited as long as it is a solid substance that can be coated with the hydrophilic thermosetting resin composition, and among them, a fiber substrate is preferable. The base material is impregnated with the hydrophilic thermosetting resin composition, or the base material surface is coated with the hydrophilic thermosetting resin composition, and after coating, the resin composition is cured. Thus, a hydrophilic molded product can be efficiently produced.

  Examples of the fiber substrate used here include fiber substrates made of insulating paper, glass cloth, carbon fiber, polyolefin fiber, nylon fiber, polyester fiber, acrylic fiber, and the like.

  In the unsaturated polyester resin composition containing the components (A) to (C), for example, the resin composition is cured at 90 to 110 ° C. for 0.5 to 2 hours, and then at 110 to 130 ° C. It is preferable to carry out heating for 0.5 to 2 hours. In addition, in the epoxy resin composition containing the components (D) to (F), for example, heating at 90 to 110 ° C. for 0.5 to 2 hours, and heating at 140 to 160 ° C. for 0.5 to 2 hours. Is preferred.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.

Example 1
16 parts by mass of maleic anhydride, 12 parts by mass of phthalic anhydride, and 16 parts by mass of ethylene glycol were subjected to a dehydration condensation reaction while heating at 200 to 230 ° C. in a nitrogen atmosphere. Dehydration under reduced pressure was performed at an acid value of 25 to obtain an unsaturated polyester resin.
40 parts by mass of the obtained unsaturated polyester resin was mixed with 60 parts by mass of 2-hydroxyethyl methacrylate (2-HEMA) together with 0.03 parts by mass of hydroquinone and diluted, and further 0.2 parts by mass of manganese naphthenate solution Was added to obtain a mixture for preparing a hydrophilic thermosetting resin composition.

  To 100.23 parts by mass of the obtained mixture for preparation, 1 part by mass of organic peroxide (manufactured by NOF Corporation, trade name: Perhexa C (S)), inorganic filler (manufactured by Tatsumori Co., Ltd., trade name: 5 parts by weight of crystallite AA) was added, and the resulting unsaturated polyester resin composition was heated at 100 ° C. for 1 hour, and then further heated and molded at 120 ° C. for 1 hour to obtain a test hydrophilicity of 50 mm × 50 mm × 5 mm. A molded product (compound) was produced.

  Moreover, 1 part by mass of an organic peroxide (manufactured by NOF Corporation, trade name: Perhexa C (S)) was added to 100.23 parts by mass of the resulting mixture for preparation, and the resulting unsaturated polyester resin composition was obtained. Is impregnated with insulating paper (DuPont, product name: Nomex), heated at 100 ° C. for 1 hour, further heated and molded at 120 ° C. for 1 hour, and cured by heating and pressing in a mold to obtain a resin component. A 60% by weight hydrophilic molded article (inorganic fiber composite) for testing was produced.

(Example 2)
Bisphenol F-type epoxy resin 100 parts by mass, allylphenol-formaldehyde resin 70 parts by mass, and a curing accelerator 1 part by mass were mixed well to obtain an epoxy resin composition as a hydrophilic thermosetting resin composition.
The obtained epoxy resin composition was heated at 100 ° C. for 1 hour, and further heated and molded at 150 ° C. for 1 hour to produce a hydrophilic molded product (compound) for testing of 50 mm × 50 mm × 5 mm.

  Further, the obtained epoxy resin composition was impregnated into insulating paper (DuPont, product name: Nomex), heated at 100 for 1 hour, further heated at 150 ° C. for 1 hour, and heated in the mold. Pressurized and cured to produce a hydrophilic molded article for testing (inorganic fiber composite) having a resin content of 60% by mass.

(Example 3 and Comparative Examples 1-6)
With the blending components shown in Table 1, a hydrophilic thermosetting resin composition and a hydrophilic molded article were produced by the same operation as in Example 1 or Example 2.

The compounding components used here are specifically as follows.
[Unsaturated polyester resin]
Unsaturated polyester resin synthesized in Example 1 [epoxy resin]
Bisphenol F type epoxy resin: manufactured by Mitsubishi Chemical Corporation, trade name: jER807
Bisphenol A type epoxy resin: manufactured by Mitsubishi Chemical Corporation, trade name: jER828

[Curing agent]
Allylphenol / formaldehyde resin: manufactured by Meiwa Kasei Co., Ltd., trade name: MEH-8000H
Polyamide polyamine resin: Sanyo Chemical Industries, Ltd., trade name: Polymide L-4051
Methyltetrahydrophthalic anhydride: Hitachi Chemical Co., Ltd., trade name: HN-2000
Methylendomethylenetetrahydrophthalic anhydride: manufactured by Nippon Kayaku Co., Ltd., trade name: Kayahard MCD
(Reactive diluent)
2-hydroxyethyl methacrylate: Mitsubishi Gas Chemical Co., Ltd., trade name: 2-HEMA
Styrene monomer: Asahi Kasei Chemicals Corporation

[Curing accelerator]
2-Heptadecylimidazole: Shikoku Kasei Co., Ltd., trade name: Curezol C17Z
(Polymerization initiator)
Peroxide: manufactured by NOF Corporation, trade name: Perhexa C (S)
[Surface treatment agent]
96% concentrated sulfuric acid: Wako Pure Chemical Industries, Ltd. [polymerization inhibitor]
Hydroquinone: Seiko Chemical Co., Ltd. [polymerization accelerator]
Manganese naphthenate solution: manufactured by DIC Corporation, trade name: Mn-NAPHENATE 6% X
[Filler]
Inorganic filler: manufactured by Tatsumori Co., Ltd., trade name: Crystallite AA (crystalline silica powder, average particle size 6 μm)

<Characteristic test>
The obtained hydrophilic thermosetting resin composition and hydrophilic molded article were measured and evaluated for viscosity, contact angle, glass transition point, elastic modulus, and abrasion resistance by the following tests. The results are shown in Table 1 together with the resin composition.

(1) Viscosity: The viscosity of the hydrophilic thermosetting resin composition at 25 ° C. was measured using an E-type viscometer.
(2) Contact angle: Using a contact angle meter, the contact angle of distilled water on the surface of the hydrophilic molded product is measured.
(3) Glass transition point: From the inflection point of the storage elastic modulus of the hydrophilic thermosetting resin composition when measured at a heating rate of 10 ° C./min using a dynamic viscoelasticity measuring device (DMS). Calculated.
(4) Elastic modulus: The elastic modulus at 40 ° C. of the surface of the hydrophilic molded product was measured using DMS.
(5) Abrasion resistance: Unsaturated polyester resin composition is heated and cured at 100 ° C. for 1 hour and 120 ° C. for 1 hour, and epoxy resin composition is heated and cured at 100 ° C. for 1 hour and 150 ° C. for 1 hour. A cast plate having a thickness of 5 mm was obtained and used as a test piece. Washing water (water pressure: 10 MPa, 0.5 to 10 h) was applied to the test piece, the appearance after the test was visually confirmed, and evaluated according to the following criteria.
Further, the hydrophilic molded products (compounds and inorganic fiber composites) obtained in Examples 1 to 3 and Comparative Examples 1 to 6 were subjected to the same abrasion resistance test and evaluated in the same manner.
Judgment criteria ○: No change, △: Concavity and convexity on part of surface, ×: Concavity and convexity on surface

  From the above, the resin composition of the present invention has a low contact angle with water on the surface of the cured product, excellent hydrophilicity, and excellent wear resistance against contact with high-pressure water and the like by having such characteristics. Can be obtained. Moreover, the molded product obtained in this way has a long product life and can provide long-term product reliability.

Claims (7)

  A hydrophilic thermosetting resin composition comprising an unsaturated polyester resin or an epoxy resin as a main component and having a contact angle with water on the surface of the cured product of 70 degrees or less.   The unsaturated polyester resin comprises (A) an unsaturated polyester resin, (B) a reactive diluent having a hydroxyl group and a carbon-carbon double bond, and (C) a polymerization initiator as essential components. The hydrophilic thermosetting resin composition according to claim 1, wherein   The hydrophilic thermosetting resin composition according to claim 2, wherein the reactive diluent (B) is 2-hydroxyethyl methacrylate.   The epoxy resin comprises (D) a liquid bisphenol type epoxy resin, (E) a phenol resin curing agent having a hydroxyl group and a carbon-carbon double bond, and (F) a curing accelerator as essential components. The hydrophilic thermosetting resin composition according to claim 1.   Furthermore, (G) a filler is included, The hydrophilic thermosetting resin composition of any one of Claims 1-4 characterized by the above-mentioned.   A hydrophilic molded article obtained by curing and molding the hydrophilic thermosetting resin composition according to any one of claims 1 to 5.   A hydrophilic molded article obtained by impregnating a fiber base material with the hydrophilic thermosetting resin composition according to any one of claims 1 to 5 and coating and then curing.